U.S. patent number 4,853,418 [Application Number 07/229,491] was granted by the patent office on 1989-08-01 for polyurethane emulsion, sheet-like porous material making use of the emulsion and production process of the material.
This patent grant is currently assigned to Dainichiseika Color & Chemicals Mfg. Co., Ltd., Ukima Colour & Chemicals Mfg. Co., Ltd.. Invention is credited to Tomoko Goto, Kazuyuki Hanada, Masashi Kashimura, Katsumi Kuriyama, Iwao Misaizu.
United States Patent |
4,853,418 |
Hanada , et al. |
August 1, 1989 |
Polyurethane emulsion, sheet-like porous material making use of the
emulsion and production process of the material
Abstract
A polyurethane emulsion is composed of an organic solvent
solution of a polyurethane resin containing silicone segments
and/or fluorocarbon segments as backbones and/or side chains and
water emulsified in the organic solvent solution. A sheet-like
porous material having a porous layer of a polyurethane resin
provided on a base material is produced by using the above
polyurethane emulsion to form the porous layer.
Inventors: |
Hanada; Kazuyuki (Washinomiya,
JP), Misaizu; Iwao (Ageo, JP), Kashimura;
Masashi (Tokyo, JP), Goto; Tomoko (Kawaguchi,
JP), Kuriyama; Katsumi (Koshigaya, JP) |
Assignee: |
Dainichiseika Color & Chemicals
Mfg. Co., Ltd. (Tokyo, JP)
Ukima Colour & Chemicals Mfg. Co., Ltd. (Tokyo,
JP)
|
Family
ID: |
16389155 |
Appl.
No.: |
07/229,491 |
Filed: |
August 8, 1988 |
Foreign Application Priority Data
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Aug 10, 1987 [JP] |
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62-198320 |
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Current U.S.
Class: |
521/154; 524/588;
521/170; 524/591; 524/731; 524/700 |
Current CPC
Class: |
C08G
18/2885 (20130101); C08G 18/289 (20130101); C08G
18/61 (20130101); C08J 3/09 (20130101); C08J
9/283 (20130101); D06N 3/14 (20130101); C08J
2375/04 (20130101) |
Current International
Class: |
D06N
3/14 (20060101); D06N 3/12 (20060101); C08J
9/00 (20060101); C08G 18/00 (20060101); C08J
9/28 (20060101); C08G 18/28 (20060101); C08J
3/09 (20060101); C08J 3/02 (20060101); C08G
18/61 (20060101); C08G 018/14 () |
Field of
Search: |
;521/154,170
;524/588,591,700,731 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
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|
|
1294711 |
|
Nov 1972 |
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GB |
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1501244 |
|
Feb 1978 |
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GB |
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2009192 |
|
Jun 1979 |
|
GB |
|
Primary Examiner: Welsh; Maurice J.
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier
& Neustadt
Claims
We claim:
1. A polyurethane emulsion comprising:
an organic solvent solution of a polyurethane resin containing
silicone segments and/or fluorocarbon segments as backbones and/or
side chains; and
water emulsified in the organic solvent solution.
2. The polyurethane emulsion as claimed in claim 1, wherein the
silicone segments and fluorocarbon segments amount to 0.2-50 wt.%
of the whole polyurethane resin.
3. In a sheet-like porous material having a porous layer of a
polyurethane resin provided on a base material, the improvement
wherein the polyurethane resin has silicone segments and/or
fluorocarbon segments as backbones and/or side chains.
4. The sheet-like porous material as claimed in claim 3, wherein
the silicone segments and fluorocarbon segments amount to 0.2-50
wt.% of the whole polyurethane resin.
5. In a process for producing a sheet-like porous material by
impregnating and/or coating a base material with a water-in-oil
type polyurethane emulsion and then gelling and drying the
emulsion, the improvement wherein the polyurethane emulsion
comprises:
an organic solvent solution of a polyurethane resin containing
silicone segments and/or fluorocarbon segments as backbones and/or
side chains; and
water emulsified in the organic solvent solution.
6. The process as claimed in claim 5, wherein the silicone segments
and fluorocarbon segments amount to 0.2-50 wt.% of the whole
polyurethane resin.
Description
BACKGROUND OF THE INVENTION
(1) Field of the Invention
This invention relates to a polyurethane emulsion, a sheet-like
porous material and a production process of the porous material. It
is a primary object of this invention to provide a sheet-like
porous material which is excellent in various properties such as
surface smoothness, water repellancy (withstandable water
pressure), stain resistance, washability, mechanical properties and
vapor permeability and is also good in hand and feel.
(2) Description of the Related Art
Numerous sheet-like porous materials composed of a polyurethane
resin and suited as a natural leather substitute have heretofore
been known. A number of processes has also been known as their
production processes. These processes may be divided roughly into
wet processes and dry processes.
These processes are each accompanied by both merits and demerits
and dry processes are superior from the standpoint of productivity.
As such dry processes, there are known those described in Japanese
Patent Publication Nos. 4380/1973 and 8742/1973, Japanese Patent
Laid-Open Nos. 41063/1976, 66961/1979 and 68498/1979, etc.
Although sheet-like porous materials having excellent vapor
permeability can be provided by these known processes, these
sheet-like porous materials has a porous structure and corollary to
this, is accompanied by drawbacks that they are inferior in surface
smoothness, hand and feeling and are prone to staining.
These sheet-like porous materials contain through pores in order to
have moisture permeability. As a result, they are accompanied by a
further drawback that penetration of external water is easy and
when they are used on a rainy day or the like, water penetrates to
the inside and the inside is thus wet.
As a method for solving such drawbacks, it is widely practised to
incorporate so-called flexibilizer and water repellant, such as
fluorocarbon compound and fluorine compound, in the porous layer.
Such flexibilizer and water repellant are compounds having a
relatively low molecular weight and have poor compatibility with
polyurethane resins. They hence tend to bleed out to the surface of
the porous layer, thereby causing a staining problem that the
surface becomes sticky and more susceptible to dust deposition.
Furthermore, the flexibilizer and water repellant are washed away
when the sheet-like porous material is washed repeatedly, leading
to a problem in washability that the properties imparted by the
flexibilizer and water repellant, such as surface smoothness, hand
and feeling, water repellancy (withstandable water pressure) and
stain resistance, would be lost.
There is hence an outstanding demand for the development of a
sheet-like porous material which has good surface smoothness, hand
and feeling and excellent withstandable water pressure, stain
resistance and washability in spite of its porous structure.
SUMMARY OF THE INVENTION
The present inventors have carried out an extensive investigation
with a view toward meeting the above demand. As a result, it has
been found that the use of a specific polyurethane emulsion can
solve drawbacks of the conventional techniques, such as those
mentioned above, and can thus provide a sheet-like porous material
capable of fully meeting the abovementioned demand in the present
field of art.
Namely, it has been revealed that the abovedescribed problems of
the conventional art can be solved by using a specific
polyurethane, namely, a polyurethane resin containing silicone
segments and/or fluorocarbon segments as backbones and/or side
chains for the formation of a porous layer.
In one aspect of this invention, there is thus provided a
polyurethane emulsion which comprises:
an organic solvent solution of a polyurethane resin containing
silicone segments and/or fluorocarbon segments as backbones and/or
side chains; and
water emulsified in the organic solvent solution.
In another aspect of this invention, there is also provided a
sheet-like porous material having a porous layer of a polyurethane
resin provided on a base material, in which the polyurethane resin
has silicone segments and/or fluorocarbon segments as backbones
and/or side chains.
In a further aspect of this invention, there is also provided a
process for producing a sheet-like porous material by impregnating
and/or coating a base material with a water-in-oil type
polyurethane emulsion and then gelling and drying the emulsion. The
polyurethane emulsion comprises:
an organic solvent solution of a polyurethane resin containing
silicone segments and/or fluorocarbon segments as backbones and/or
side chains; and
water emulsified in the organic solvent solution.
In the present invention, silicone compound and/or fluorine
compound as flexibilizer(s) and/or water repellant(s) are bound by
covalent bonds in the polyurethane. As a result, even after the
polyurethane is formed into a porous layer, the flexibilizer(s)
and/or water repellant(s) do not bleed out to the surface along the
passage of time and are not washed away by washing, so that
excellent surface smoothness and high flexibility, withstandable
water pressure, stain resistance and washability can be retained
almost permanently.
The above and other objects, features and advantages of the present
invention will become apparent form the following description of
the invention and the appended claims.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
The polyurethane resin, which is employed in this invention,
primarily features this invention and contains silicone segments
and/or fluorocarbon segments, is obtained by using a silicone
compound having one or more reactive functional groups such as
amino, epoxy, hydroxyl, carboxyl and/or thioalcohol groups and/or a
fluorine compound having one or more of such functional groups as
the entire or partial portion of a polyol, polyisocyanate or chain
extender upon obtaining a polyurethane resin by reacting the
polyol, polyisocyanate, chain extender, etc.
Upon synthesis of the polyurethane resin in the above-described
manner, it is possible to synthesize a polyurethane resin
containing silicone segments from a silicone compound with one or
more reactive functional groups and also another polyurethane resin
containing fluorocarbon segments and then to mix and use them at a
suitable ratio.
As preferred examples of the silicone compound having one or more
reactive organic functional groups as described above, the
following compounds may be mentioned by way of example.
(1) Amino-modified silicone oils: ##STR1##
(2) Epoxy-modified silicone oils: ##STR2##
(3) Alcohol-modified silicone oils: ##STR3##
(4) Mercapto-modified silicone oils: ##STR4##
(5) Carboxyl-modified silicone oils: ##STR5##
The following compounds may be mentioned as exemplary fluorocarbon
compounds containing such reactive functional groups as described
above.
(1) H(CF.sub.2 CF.sub.2).sub.n CH.sub.2 OH (n: 1-7)
(2) CF.sub.3 (CF.sub.2 CF.sub.2).sub.n CH.sub.2 CH.sub.2 OH (n:
1-10)
(3) CF.sub.3 (CF.sub.2 CF.sub.2).sub.n COOH (n: 1-10)
(4) CF.sub.3 (CF.sub.2 CF.sub.2).sub.n CH.sub.2 CH.sub.2 SH (n:
1-10)
(5) H(CF.sub.2 CF.sub.2).sub.l (CH.sub.2).sub.m (OCH.sub.2 CH.sub.2
(OH)CH.sub.2).sub.n OH (l: 1-10, m: 1-10, n: 1-3)
(6) F(CF.sub.2 CF.sub.2).sub.l (CH.sub.2).sub.m (OCH.sub.2 CH.sub.2
(OH)CH.sub.2).sub.n OH (l: 1-10, m: 1-10, n: 1-3) ##STR6## (R:
hydrogen or fluorine atom, k: 2-16, l: 0-6, m: 0-3, n: 1-3)
The above silicone compounds and fluorocarbon compounds, which
contain such reactive organic functional groups as described above,
are merely illustrative compounds preferred in the present
invention. It should therefore borne in mind that the present
invention is not limited to the use of such exemplified compounds.
The above exemplified compounds and other compounds are currently
sold on the market and hence readily available there. They are all
usable in the present invention.
Intermediates obtained respectively by reacting such silicone
compounds and/or fluorocarbon compounds and polyisocyanates, which
will be described subsequently, in such a way that at least either
the reactive groups of the silicone compounds and/or fluorocarbon
compounds or the isocyanate groups of he polyisocyanates are
allowed to remain, for example, those obtained respectively by
reacting bifunctional silicone compounds and/or fluorocarbon
compounds and polyfunctional polyisocyanates at a ratio of excess
isocyanate groups or on the contrary, those obtained respectively
by reacting them at a ratio of excess reactive groups of the
bifunctional silicone compounds and/or fluorocarbon compounds may
be used similarly.
Where the reactive groups of silicone compounds and/or fluorocarbon
compounds are hydroxyl groups, amino groups, carboxyl groups, epoxy
groups and/or the like, polyesterpolyols, polyamidepolyamines,
polyetherpolyols and the like obtained by reacting them with the
below-described polyols, chain extenders, polycarboxylic acids or
polyamines may also be used similarly.
Conventionally-known polyols for polyurethanes can all be used as
polyols. Preferred examples may include those containing a hydroxyl
group as a terminal group and having a molecular weight of
300-4,000, such as:
Polyethylene adipate,
Polyethylenepropylene adipate,
Polyethylenebutylene adipate,
Polydiethylene adipate,
Polybutylene adipate,
Polyethylene succinate,
Polybutylene succinate,
Polyethylene sebacate,
Polybutylene sebacate,
Polytetramethylene ether glycol,
Poly-.epsilon.-caprolatonediol,
Polyhexamethylene adipate,
Carbonatepolyol,
Polypropylene glycol, etc.
Those containing polyoxyethylene chains in a suitable proportion in
the above-exemplified polyols may also be mentioned as preferred
polyols.
Conventionally-known organic polyisocyanates may all be used. The
following polyisocyanates may be mentioned as preferred
examples.
4,4'-Diphenylmethane diisocyanate (MDI),
Hydrogenated MDI,
Isophorone diisocyanate,
1,3-Xylylene diisocyanate,
1,4-Xylylene diisocyanate,
2,4-Tolylene diisocyanate,
2,6-Tolylene diisocyanate,
1,5-Naphthalene diisocyanate,
m-Phenylene diisocyanate,
p-Phenylene diisocyanate, etc.
Needless to say, it is also possible to use urethane prepolymers
obtained by reacting these organic polyisocyanates and low
molecular polyols or polyamines in such a way that terminal
isocyanates are formed.
Although conventionally-known chain extenders can all be used, the
following chain extenders may be mentioned as preferred
examples.
Ethylene glycol,
Propylene glycol,
Diethylene glycol,
1,4-Butanediol,
1,6-Hexanediol,
Ethylenediamine,
1,2-Propylenediamine,
Trimethylenediamine,
Tetramethylenediamine,
Hexamethylenediamine,
Decamethylenediamine,
Isophoronediamine,
m-Xylylenediamine,
Hydrazine,
Water, etc.
Polyurethane resins containing silicone segments and/or
fluorocarbon segments and blends of polyurethane resins containing
silicone segments and polyurethane resins containing fluorocarbon
segments, which are obtained from such materials as mentioned
above, are all usable in the present invention. Among these,
preferred are those containing silicon segments and/or fluorocarbon
segments in a proportion of about 0.2-50 wt.% of the resins. If the
total proportion of silicon segments and/or fluorocarbon segments
is smaller than about 0.2 wt.%, such a proportion is too small to
achieve the objects of the present invention. On the other hand,
any proportions greater than about 50 wt.% are not preferred
because they result in problems such as reduced adhesion to base
materials.
Their molecular weights may preferably range from 20,000 to
500,000, with 20,000-250,000 being most preferred.
Such polyurethane resins containing silicone segments and/or
fluorocarbon segments can be easily obtained by any one of
production processes known to date. These polyurethane resins may
be prepared without any solvent or may be prepared in an organic
solvent. From the process standpoint, it is advantageous to prepare
them in an organic solvent useful for the preparation of
polyurethane emulsions, in other words, in an organic solvent
having a certain degree of miscibility with water, because the
resulting reaction mixture may be used as is for the preparation of
a polyurethane emulsion.
Preferable examples of such an organic solent may include methyl
ethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone,
diethyl ketone, methyl formate, ethyl formate, propyl formate,
methyl acetate, ethyl acetate, butyl acetate and the like. It is
also feasible to use acetone, cyclohexanone, tetrahydrofuran,
dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene,
xylene, dimethylformamide, dimethylsulfoxide, perchloroethylene,
trichloroethylene, methylcellosolve, butylcellosolve, cellosolve
acetate, and the like. Among these organic solvents, those miscible
with water without limitations or those insoluble in water are used
by mixing them with other solvents and hence imparting a limitation
to their miscibility with water. The above-described organic
solvents may of course be used as mixed organic solvents.
When a polyurethane resin is prepared in such an organic solvent,
the polyurethane resin is obtained in the form of a solution. It is
convenient to adjust the solid content to a range of about 5-60
wt.% by either adding a solvent of the same or different type or
removing the solvent. In the present invention, the polyurethane
resin may be dissolved fully in the organic solvent or may be in
the form of a dispersion in which it is contained partially or
wholly as crystals. They will hereinafter be called "solutions" for
the sake of brevity.
In order to prepare a polyurethane emulsion from the
above-described polyurethane solution, a suitable amount of a
water-in-oil type emulsifier is added to the polyurethane solution
as needed. While vigorously stirring the resultant mixture, water
is added in a proportion less than the saturation, for example, in
an amount of about 50-500 parts by weight per 100 parts by solids
weight of solution so that the polyurethane emulsion is
obtained.
Any one of water-in-oil type emulsifiers known to date may be used
as an emulsifier. Particularly preferred are polyurethane-based
interface lubricants containing polyoxyethylene chains in a
suitable proportion in the molecule. The emulsifier may be used
preferably in a proportion of about 1-10 parts by weight per 100
parts by solids weight of the polyurethane resin solution.
The thus-obtained polyurethane emulsion is a cream-like fluid of a
milky white color. It retains its stable state even when it is left
over for several months as is. Such a polyurethane emulsion may be
added with one or more of various additives, for example, additives
known conventionally such as colorants, crosslinking agents,
stabilizers and fillers, as needed.
As a base material usable upon production of a sheet-like porous
material by using such a polyurethane emulsion, any base material
may be employed, for example, a desired one of various woven
fabrics, knitted fabrics, non-woven fabrics, parting papers,
plastic films, metal plates, glass plates and the like.
For the application of the polyurethane emulsion to the base
material, any known method may be used such as a coating technique,
a dipping technique or a combination thereof. The amount of the
polyurethane emulsion to be employed for impregnation and/or
coating may vary in a wide range, for example, about 2-2,000 g
(wet) per m.sup.2 depending what end use will be made.
The gelling of the polyurethane emulsion applied on the base
material and the drying of the thus-gelled polyurethane emulsion
and the impregnated and/or coated base material can be achieved in
much the same way as the prior art. For example, a sheet-like
porous polyurethane material having excellent properties can be
obtained by drying the impregnated or coated base material at a
temperature of about 40.degree.-200.degree. C. or so.
The sheet-like porous material obtained by using such a
polyurethane emulsion according to this invention has a very fine
porous structure, has various excellent physical properties along
with superb vapor permeability, and is hence useful as a sheet
stock for various synthetic leathers and the like, in particular,
as apparel, shoes, waterproof fabric, tents, wall paper, flooring,
filter materials, filters for air conditioners, and the like.
It is worthy to note that the polyurethane resin in the
polyurethane emulsion according to this invention contains silicone
segments and/or fluorocarbon segments in the backbone and/or side
chains of its molecule. As a result, even after the formation of a
porous layer from the emulsion, the silicone segments and/or
fluorocarbon segments in the porous layer do not bleed out to the
surface of the porous layer along the passage of time, so that the
sheet-like porous material can semi-permanently maintain the
excellent surface smoothness, hand and feeling, withstandable water
pressure, stain resistance and washability.
The present invention will hereinafter be described specifically by
the following Referential Examples, Examples and Comparative
Examples, in which all designations of "part" or "parts" and "%"
mean part or parts by weight and wt.% unless otherwise specifically
indicated.
REFERENTIAL EXAMPLE 1: (PREPARATION OF INTERMEDIATE)
While thoroughly stirring at 50.degree. C. 175 parts of a 1:3 (by
molar ratio) adduct of trimethylolpropane and tolylenediisocyanate
(TDI) ("Colonate L", trade name; product of Nippon Polyurethane
Industry Co., Ltd.; NCO %: 12.5; solids: 75%), 880 parts of an
aminopropylterminated polydimethylsiloxane (molecular weight:
2,200) having the following structural formula were gradually added
dropwise to the adduct so as to react them to each other. ##STR7##
(n: a value to give the molecular weight of 2,200)
After completion of the reaction, ethyl acetate was caused to
evaporate so that 976 parts of an intermediate were obtained in the
form of a clear liquid.
An infrared absorption spectrum of the intermediate still indicated
an absorption by free isocyanate groups at 2270 cm.sup.-1. Another
absorption by Si--O--C groups was also observed at 1090
cm.sup.-1.
As a result of a quantitative analysis of the free isocyanate
groups in the intermediate, their content was found to be 0.78%
while its calculated value was 0.83%.
Accordingly, the basic structure of the intermediate is estimated
to have the following formula. ##STR8##
REFERENTIAL EXAMPLE 2: (PREPARATION OF INTERMEDIATE)
Twenty-four parts of phenyl isocyanate were added to 196 parts of a
hydroxypropyl-terminated polydimethylsiloxane (molecular weight:
980) having the below-described structure. They were reacted to
each other at 60.degree. C. under thorough stirring, thereby
obtaining 213 parts of a reaction product in the form of a clear
liquid. ##STR9## (n: a value to give the molecular weight of
980)
While thoroughly stirring at 60.degree. C. 52 parts of a
hexamethylene diisocyanate-water adduct ("Duranate 24A-100", trade
name; product of Asahi Chemical Industry CO., Ltd.; NOC %: 23.5),
220 parts of the above reaction product were gradually added
dropwise to the adduct so as to react them to each other, whereby
263 parts of an intermediate were obtained in the form of a
colorless clear liquid.
An infrared absorption spectrum of the intermediate still indicated
an absorption by free isocyanate groups at 2270 cm.sup.-1. Another
absorption by Si--O--C groups was also observed at 1090
cm.sup.-1.
As a result of a quantitative analysis of the free isocyanate
groups in the intermediate, their content was found to be 1.37%
while its calculated value was 1.54%.
Accordingly, the basic structure of the intermediate is estimated
to have the following formula. ##STR10##
REFERENTIAL EXAMPLE 3: (PREPARATION OF INTERMEDIATE)
Fifteen parts of n-butylaldehyde were added to 230 parts of an
aminopropyl-terminated polydimethylsiloxane (molecular weight:
1,150) having the below-described structure. They were reacted to
each other at 80.degree. C. for 3 hours under thorough stirring
while taking the resulting water out of the system, thereby
obtaining 238 parts of a reaction product in the form of a clear
liquid. ##STR11## (n: a value to give the molecular weight of
1,150)
While thoroughly stirring at room temperature 186 parts of a 1:3
(by molar ratio) adduct of trimethylol propane and xylylene
diisocyanate ("Takenate D110N", trade name; product of Takeda
Chemical Industries, Ltd.; NCO %: 11.5; solids: 75%), 490 parts of
the above reaction product were gradually added dropwise to the
adduct so as to react them to each other.
After completion of the reaction, ethyl acetate was caused to
evaporate so that 610 parts of an intermediate were obtained in the
form of a clear liquid.
An infrared absorption spectrum of the intermediate still indicated
an absorption by free isocyanate groups at 2270 cm.sup.-1. Another
absorption by Si--O--C groups was also observed at 1090
cm.sup.-1.
As a result of a quantitative analysis of the free isocyanate
groups in the intermediate, their content was found to be 1.25%
while its calculated value was 1.34%.
Accordingly, the basic structure of the intermediate is estimated
to have the following formula. ##STR12##
REFERENTIAL EXAMPLE 4: (Preparation of Intermediate)
While thoroughly stirring at 60.degree. C. 35 parts of 2,6-tolylene
diisocyanate and 110 parts of ethyl acetate, 316 parts of a
mercaptopropyl-terminated polydimethylsiloxane (molecular weight:
1,580) having the following structural formula were gradually added
dropwise to the adduct so as to react them to each other. ##STR13##
(l, m, n: values to give the molecular weight of 1,580)
After completion of the reaction, the ethyl acetate was caused to
evaporate so that 340 parts of an intermediate were obtained in the
form of a clear liquid.
An infrared absorption spectrum of the intermediate still indicated
an absorption by free isocyanate groups at 2270 cm.sup.-1. Another
absorption by Si--O--C groups was also observed at 1090
cm.sup.-1.
As a result of a quantitative analysis of the free isocyanate
groups in the intermediate, their content was found to be 2.12%
while its calculated value was 2.39%.
Accordingly, the basic structure of the intermediate is estimated
to have the following formula. ##STR14##
REFERENTIAL EXAMPLE 5: (Preparation of Intermediate)
While thoroughly stirring at 60.degree. C. 160 parts of
hexamethylene diisocyanate and 160 parts of ethyl acetate, 450
parts of a hydroxylpropyl-terminated polydimethylsiloxane
(molecular weight: 2,250) having the following structural formula
were gradually added dropwise to the adduct so as to react them to
each other. ##STR15## (n: a value to give the molecular weight of
2,250)
After completion of the reaction, the ethyl acetate was caused to
evaporate so that 488 parts of an intermediate were obtained in the
form of a clear liquid.
An infrared absorption spectrum of the intermediate still indicated
an absorption by free isocyanate groups at 2270 cm.sup.-1. Another
absorption by Si--O--C groups was also observed at 1090
cm.sup.-1.
As a result of a quantitative analysis of the free isocyanate
groups in the intermediate, their content was found to be 1.52%
while its calculated value was 1.67%.
Accordingly, the basic structure of the intermediate is estimated
to have the following formula. ##STR16##
REFERENTIAL EXAMPLE 6: (Preparation of Intermediate)
While thoroughly stirring at 60.degree. C. 52 parts of the
hexamethylene diisocyanate-water adduct ("Duranate 24A-100", trade
name; product of Asahi Chemical Industry Co., Ltd.; NOC %: 23.5),
53 parts of a fluorinated alcohol having the below-described
structure were gradually added dropwise to the adduct so as to
react them to each other, whereby 103 parts of an intermediate were
obtained in the form of a colorless clear liquid.
An infrared absorption spectrum of the intermediate still indicated
an absorption by free isocyanate groups at 2270 cm.sup.-1. Another
absorption by --CF.sub.2 -- groups was also observed at 1190
cm.sup.-1. As a result of a quantitative analysis of the free
isocyanate groups in the intermediate, their content was found to
be 2.65% while its calculated value was 2.51%.
Accordingly, the basic structure of the intermediate is estimated
to have the following formula. ##STR17##
REFERENTIAL EXAMPLE 7: (Preparation of Intermediate)
While thoroughly stirring at 50.degree. C. 120 parts of the 1:3 (by
molar ratio) adduct of trimethylolpropane and tolylenediisocyanate
(TDI) ("Colonate L", trade name; product of Nippon Polyurethane
Industry Co., Ltd.; NCO %: 12.5; solids: 75%), 114 parts of a
fluorinated alcohol having the below-described structure were
gradually added dropwise to the adduct so as to react them to each
other.
After completion of the reaction, 198 parts of an intermediate were
obtained in the form of a clear liquid.
An infrared absorption spectrum of the intermediate still indicated
an absorption by free isocyanate groups at 2270 cm.sup.-1. Another
absorption by --CF.sub.2 -- groups was also observed at 1190
cm.sup.-1. As a result of a quantitative analysis of the free
isocyanate groups in the intermediate, their content was found to
be 2.68% while its calculated value was 2.83%.
Accordingly, the basic structure of the intermediate is estimated
to have the following formula. ##STR18##
REFERENTIAL EXAMPLE 8: (Preparation of Intermediate)
While thoroughly stirring at room temperature 186 parts of the 1:3
(by molar ratio) adduct of trimethylol propane and xylylene
diisocyanate ("Takenate D110N", trade name; product of Takeda
Chemical Industries, Ltd.; NCO %: 11.5; solids: 75%), 172 parts of
a fluorinated thiol having the below-described structure were
gradually added dropwise to the adduct so as to react them to each
other.
After completion of the reaction, 320 parts of an intermediate were
obtained in the form of a clear liquid.
An infrared absorption spectrum of the intermediate still indicated
an absorption by free isocyanate groups at 2270 cm.sup.-1. Another
absorption by --CF.sub.2 -- groups was also observed at 1190
cm.sup.-1. As a result of a quantitative analysis of the free
isocyanate groups in the intermediate, their content was found to
be 2.51% while its calculated value was 2.69%.
Accordingly, the basic structure of the intermediate is estimated
to have the following formula. ##STR19##
REFERENTIAL EXAMPLE 9
(Modification of Resin Side Chains)
After reacting 1,000 parts of polyethylene adipate (average
molecular weight: about 1,000; hydroxyl number: 112), 144 parts of
1,4-butanediol, 1,144 parts of methyl ethyl ketone and 650 parts of
diphenylmethane diisocyanate at 70.degree. C. for 8 hours, 3,042
parts of methyl ethyl ketone were added further. The resultant
mixture was rendered uniform and then cooled to room temperature
under stirring, thereby obtaining a milky white polyurethane
dispersion having a solid content of 30%.
Five parts of the intermediate of Referential Example 1 were added
to 100 parts of the above polyurethane dispersion. They were
reacted at 70.degree. C. for 4 hours to obtain a milky white
solution [hereinafter called "Modified Resin Solution (1)"] of a
modified resin in which the intermediate and polyurethane resin
were coupled together.
No isocyanate groups were observed by an infrared absorption
analysis of the modified resin obtained above. This indicates that
the intermediate was grafted on the resin.
REFERENTIAL EXAMPLE 10
(Modification of Resin Side Chains)
After reacting 1,000 parts of 1,4-butaneethylene adipate (average
molecular weight: about 1,000; hydroxyl number: 112), 144 parts of
1,4-butanediol, 1,144 parts of methyl ethyl ketone and 650 parts of
diphenylmethane diisocyanate at 70.degree. C. for 8 hours, 3,042
parts of methyl ethyl ketone were added further. The resultant
mixture was rendered uniform and then cooled to room temperature
under stirring, thereby obtaining a milky white polyurethane
dispersion having a solid content of 30%.
Five parts of the intermediate of Referential Example 2 were added
to 100 parts of the above polyurethane dispersion. They were
reacted at 70.degree. C. for 4 hours to obtain a milky white
solution [hereinafter called "Modified Resin Solution (2)"] of a
modified resin in which the intermediate and polyurethane resin
were coupled together.
No isocyanate groups were observed by an infrared absorption
analysis of the modified resin obtained above. This indicates that
the intermediate was grafted on the resin.
REFERENTIAL EXAMPLE 11
(Modification of Resin Side Chains)
After reacting 1,000 parts of 1,6-hexamethylene adipate (average
molecular weight: about 2,000; hydroxyl number: 56), 125 parts of
1,4-butanediol, 1,200 parts of methyl ethyl ketone and 427 parts of
diphenylmethane diisocyanate at 70.degree. C. for 8 hours, 2,526
parts of methyl ethyl ketone were added further. The resultant
mixture was rendered uniform and then cooled to room temperature
under stirring, thereby obtaining a milky white polyurethane
dispersion having a solid content of 30%.
Five parts of the intermediate of Referential Example 3 were added
to 100 parts of the above polyurethane dispersion. They were
reacted at 70.degree. C. for 4 hours to obtain a milky white
solution [hereinafter called "Modified Resin Solution (3)"] of a
modified resin in which the intermediate and polyurethane resin
were coupled together.
No isocyanate groups were observed by an infrared absorption
analysis of the modified resin obtained above. This indicates that
the intermediate was grafted on the resin.
REFERENTIAL EXAMPLE 12
(Modification of Resin Side Chains)
After reacting 1,000 parts of polytetramethylene glycol (average
molecular weight: about 1,000; hydroxyl number: 112), 93 parts of
ethylene glycol, 1,500 parts of methyl ethyl ketone and 625 parts
of diphenylmethane diisocyanate at 70.degree. C. for 8 hours, 2,500
parts of methyl ethyl ketone were added further. The resultant
mixture was rendered uniform and then cooled to room temperature
under stirring, thereby obtaining a milky white polyurethane
dispersion having a solid content of 30%.
Five parts of the intermediate of Referential Example 4 were added
to 100 parts of the above polyurethane dispersion. They were
reacted at 70.degree. C. for 4 hours to obtain a milky white
solution [hereinafter called "Modified Resin Solution (4)"] of a
modified resin in which the intermediate and polyurethane resin
were coupled together.
No isocyanate groups were observed by an infrared absorption
analysis of the modified resin obtained above. This indicates that
the intermediate was grafted on the resin.
REFERENTIAL EXAMPLE 13
(Modification of Resin Side Chains)
After reacting 1,000 parts of polycarbonate polyol (average
molecular weight: about 2,000; hydroxyl number: 56), 86 parts of
ethylene glycol, 1,200 parts of methyl ethyl ketone and 509 parts
of diphenylmethane diisocyanate at 70.degree. C. for 8 hours, 2,522
parts of methyl ethyl ketone were added further. The resultant
mixture was rendered uniform and then cooled to room temperature
under stirring, thereby obtaining a milky white polyurethane
dispersion having a solid content of 30%.
Five parts of the intermediate of Referential Example 5 were added
to 100 parts of the above polyurethane dispersion. They were
reacted at 70.degree. C. for 4 hours to obtain a milky white
solution [hereinafter called "Modified Resin Solution (5)"] of a
modified resin in which the intermediate and polyurethane resin
were coupled together.
No isocyanate groups were observed by an infrared absorption
analysis of the modified resin obtained above. This indicates that
the intermediate was grafted on the resin.
REFERENTIAL EXAMPLE 14
(Modification of Resin Backbone)
Added to 3,600 parts of methyl ethyl ketone were 1,000 parts of
1,4-butaneethylene adipate (average molecular weight: about 1,000;
hydroxyl number: 112), 100 parts of a silicone compound of the
below-described structure, 31 parts of 1,4-butanediol and 362 parts
of diphenylmethane diisocyanate, followed by a reaction at
70.degree. C. for 8 hours to obtain a solution of a polyurethane
resin having an average molecular weight of 64,000. The solid
content of the solution was 30%.
Thereafter, 130 parts of ethylene glycol and 503 parts of
diphenylmethane diisocyanate were added to the above resin
solution. After reacting them at 60.degree. C. for 10 hours, 1,477
parts of methyl ethyl ketone were added further. The resultant
mixture was rendered uniform and then cooled to room temperature
under stirring, thereby obtaining a milky white dispersion
[hereinafter called "Polyurethane Dispersion (6)"] of a
polyurethane having an average molecular weight of 133,000. The
particle sizes of particles formed therein were not greater than 1
.mu.m. The solid content of the dispersion was 30%. ##STR20## (n: a
value to give a molecular weight of 5,000)
REFERENTIAL EXAMPLE 15
(Modification of Resin Backbone)
Added to 3,580 parts of methyl ethyl ketone were 1,000 parts of
polytetramethylene glycol (average molecular weight: about 1,000;
hydroxyl number: 112), 100 parts of a silicone compound of the
below-described structure, 24 parts of ethylene glycol and 360
parts of diphenylmethane diisocyanate, followed by a reaction at
70.degree. C. for 9 hours to obtain a solution of a polyurethane
resin having an average molecular weight of 53,000. The solid
content of the solution was 30%.
Thereafter, 116 parts of ethylene glycol and 465 parts of
diphenylmethane diisocyanate were added to the above resin
solution. After reacting them at 60.degree. C. for 10 hours, 1,356
parts of methyl ethyl ketone were added further. The resultant
mixture was rendered uniform and then cooled to room temperature
under stirring, thereby obtaining a milky white dispersion
[hereinafter called "Polyurethane Dispersion (7)"] of a
polyurethane having an average molecular weight of 107,000. The
particle sizes of particles formed therein were not greater than 1
.mu.m. The solid content of the dispersion was 30%. ##STR21## (n: a
value to give a molecular weight of 5,000)
REFERENTIAL EXAMPLE 16
(Modification of Resin Backbone)
Added to 6,135 parts of methyl ethyl ketone were 2,000 parts of
1,6-hexamethylene adipate (average molecular weight: about 2,000;
hydroxyl number: 56), 200 parts of a silicone compound of the
below-described structure, 31 parts of 1,4-butanediol and 346 parts
of diphenylmethane diisocyanate, followed by a reaction at
70.degree. C. for 9 hours to obtain a solution of a polyurethane
resin having an average molecular weight of 72,000. The solid
content of the solution was 30%.
Thereafter, 390 parts of trimethylolpropane and 1,047 parts of
diphenylmethane diisocyanate were added to the above resin
solution. After reacting them at 60.degree. C. for 10 hours, 3,353
parts of methyl ethyl ketone were added further. The resultant
mixture was rendered uniform and then cooled to room temperature
under stirring, thereby obtaining a milky white dispersion
[hereinafter called "Polyurethane Dispersion (8)"] of a
polyurethane having an average molecular weight of 178,000. The
solid content of the dispersion was 30%. ##STR22## (n: a value to
give a molecular weight of 5,000)
REFERENTIAL EXAMPLE 17
(Modification of Resin Backbone)
Added to 3,435 parts of methyl ethyl ketone were 1,000 parts of
1,4-butaneethylene adipate (average molecular weight: about 1,000;
hydroxyl number: 112), 200 parts of a silicone compound of the
below-described structure, 31 parts of 1,4-butanediol and 338 parts
of diphenylmethane diisocyanate, followed by a reaction at
70.degree. C. for 8 hours to obtain a solution of a polyurethane
resin having an average molecular weight of 55,000. The solid
content of the solution was 30%.
Thereafter, 130 parts of ethylene glycol and 542 parts of
diphenylmethane diisocyanate were added to the above resin
solution. After reacting them at 60.degree. C. for 10 hours, 1,526
parts of methyl ethyl ketone were added further. The resultant
mixture was rendered uniform and then cooled to room temperature
under stirring, thereby obtaining a milky white dispersion
[hereinafter called "Polyurethane Dispersion (9)"] of a
polyurethane having an average molecular weight of 112,000. The
solid content of the dispersion was 30%. ##STR23## (n: a value to
give a molecular weight of 5,000)
REFERENTIAL EXAMPLES 18-33
Modified polyurethane resin solutions were obtained in a similar
manner as in Referential Examples 9-16 except that fluorocarbon
compounds and mixtures of fluorocarbon compounds and silicone
compounds, which are all given below in Table 1, were used
respectively in place of the silicone compounds.
TABLE 1
__________________________________________________________________________
Number of Ref. Modification modified Ex. method Fluorocarbon
compound Silicone compound resin soln.
__________________________________________________________________________
18 Ref. Ex. 9 5 Parts of the inter- -- 10 mediate of Ref. Ex. 6 19
Ref. Ex. 10 5 Parts of the inter- -- 11 mediate of Ref. Ex. 7 20
Ref. Ex. 11 5 Parts of the inter- -- 12 mediate of Ref. Ex. 8 21
Ref. Ex. 12 5 Parts of the inter- -- 13 mediate of Ref. Ex. 7 22
Ref. Ex. 13 5 Parts of the inter- -- 14 mediate of Ref. Ex. 8 23
Ref. Ex. 14 50 Parts of a compound -- 15 of the below-described
structure A 24 Ref. Ex. 15 100 Parts of a com- -- 16 pound of the
below- described structure B 25 Ref. Ex. 16 100 Parts of a com- --
17 pound of the below- described structure C 26 Ref. Ex. 9 5 Parts
of the inter- 5 Parts of the inter- 18 mediate of Ref. Ex. 1
mediate of Ref. Ex. 6 27 Ref. Ex. 10 5 Parts of the inter- 5 Parts
of the inter- 19 mediate of Ref. Ex. 2 mediate of Ref. Ex. 7 28
Ref. Ex. 11 5 Parts of the inter- 5 Parts of the inter- 20 mediate
of Ref. Ex. 3 mediate of Ref. Ex. 8 29 Ref. Ex. 12 5 Parts of the
inter- 5 Parts of the inter- 21 mediate of Ref. Ex. 4 mediate of
Ref. Ex. 7 30 Ref. Ex. 13 5 Parts of the inter- 5 Parts of the
inter- 22 mediate of Ref. Ex. 5 mediate of Ref. Ex. 8 31 Ref. Ex.
14 100 Parts of a com- 50 Parts of a compound 23 pound of the
below- of the below-described described structure D structure B 32
Ref. Ex. 15 100 Parts of a com- 50 Parts of a compound 24 pound of
the below- of the below-described described structure E structure B
33 Ref. Ex. 16 200 Parts of a com- 50 Parts of a compound 25 pound
of the below- of the below-described described structure F
structure C
__________________________________________________________________________
##STR24##
Examples 1-25
The following polyurethane emulsions were prepared by mixing the
polyurethane solutions of Referential Examples 9-33 separately
along with an emulsifier, organic solvents and water in a
homomixer.
Example 1: Polyurethane Emulsion (1)
______________________________________ Polyurethane solution (1)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Xylene 20 parts Water 85 parts
______________________________________
Example 2: Polyurethane Emulsion (2)
______________________________________ Polyurethane solution (2)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Toluene 20 parts Water 80 parts
______________________________________
Example 3: Polyurethane Emulsion (3)
______________________________________ Polyurethane solution (3)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 150
parts Toluene 20 parts Water 80 parts
______________________________________
Example 4: Polyurethane Emulsion (4)
______________________________________ Polyurethane solution (4)
100 parts PO/EO Block copolymer type emulsifier 4 parts Dioxane 10
parts Toluene 10 parts Xylene 20 parts Water 70 parts
______________________________________
Example 5: Polyurethane Emulsion (5)
______________________________________ Polyurethane solution (5)
100 parts Urethane type emulsifier 1 part Methyl isobutyl ketone 20
parts Toluene 20 parts Water 75 parts
______________________________________
Example 6: Polyurethane Emulsion (6)
______________________________________ Polyurethane solution (6)
100 parts PO/EO Block copolymer type emulsifier 1 part
tetrahydrofuran 20 parts Toluene 20 parts Water 60 parts
______________________________________
Example 7: Polyurethane Emulsion (7)
______________________________________ Polyurethane solution (7)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Xylene 20 parts Water 85 parts
______________________________________
Example 8: Polyurethane Emulsion (8)
______________________________________ Polyurethane solution (8)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Toluene 20 parts Water 80 parts
______________________________________
Example 9: Polyurethane Emulsion (9)
______________________________________ Polyurethane solution (9)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 150
parts Toluene 20 parts Water 80 parts
______________________________________
Example 10: Polyurethane Emulsion (10)
______________________________________ Polyurethane solution (10)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Xylene 20 parts Water 85 parts
______________________________________
Example 11: Polyurethane Emulsion (11)
______________________________________ Polyurethane solution (11)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Toluene 20 parts Water 80 parts
______________________________________
Example 12: Polyurethane Emulsion (12)
______________________________________ Polyurethane solution (12)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 150
parts Toluene 20 parts Water 80 parts
______________________________________
Example 13: Polyurethane Emulsion (13)
______________________________________ Polyurethane solution (13)
100 parts PO/EO Block copolymer type emulsifier 4 parts Dioxane 10
parts Toluene 10 parts Xylene 20 parts Water 70 parts
______________________________________
Example 14: Polyurethane Emulsion (14)
______________________________________ Polyurethane solution (14)
100 parts Urethane type emulsifier 1 part Methyl isobutyl ketone 20
parts Toluene 20 parts Water 75 parts
______________________________________
Example 15: Polyurethane Emulsion (15)
______________________________________ Polyurethane solution (15)
100 parts PO/EO Block copolymer type emulsifier 1 part
Tetrahydrofuran 20 parts Toluene 20 parts Water 60 parts
______________________________________
Example 16: Polyurethane Emulsion (16)
______________________________________ Polyurethane solution (16)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Xylene 20 parts Water 85 parts
______________________________________
Example 17: Polyurethane Emulsion (17)
______________________________________ Polyurethane solution (17)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Toluene 20 parts Water 80 parts
______________________________________
Example 18: Polyurethane Emulsion (18)
______________________________________ Polyurethane solution (18)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Xylene 20 parts Water 85 parts
______________________________________
Example 19: Polyurethane Emulsion (19)
______________________________________ Polyurethane solution (19)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Toluene 20 parts Water 80 parts
______________________________________
Example 20: Polyurethane Emulsion (20)
______________________________________ Polyurethane solution (20)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 150
parts Toluene 20 parts Water 80 parts
______________________________________
Example 21: Polyurethane Emulsion (21)
______________________________________ Polyurethane solution (21)
100 parts PO/EO Block copolymer type emulsifier 4 parts Dioxane 10
parts Toluene 10 parts Xylene 20 parts Water 70 parts
______________________________________
Example 22: Polyurethane Emulsion (22)
______________________________________ Polyurethane solution (22)
100 parts Urethane type emulsifier 1 part Methyl isobutyl ketone 20
parts Toluene 20 parts Water 75 parts
______________________________________
Example 23: Polyurethane Emulsion (23)
______________________________________ Polyurethane solution (23)
100 parts PO/EO Block copolymer type emulsifier 1 part
Tetrahydrofuran 20 parts Toluene 20 parts Water 60 parts
______________________________________
Example 24: Polyurethane Emulsion (24)
______________________________________ Polyurethane solution (24)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Xylene 20 parts Water 85 parts
______________________________________
Example 25: Polyurethane Emulsion (25)
______________________________________ Polyurethane solution (25)
100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20
parts Toluene 20 parts Water 80 parts
______________________________________
Comparative Examples 1-9
Polyurethane emulsions of Comparative Examples 1-9 were prepared in
a similar manner as in Examples 1-9 except that polyurethane resin
solutions obtained in the same manner as in Referential Examples
9-17 but containing no silicone segments were used respectively
instead of the polyurethane resins containing silicone
segments.
Properties of the polyurethane emulsions of Examples 1-25 and
Comparative Examples 1-9 are summarized in Table 2.
TABLE 2 ______________________________________ Viscosity Solid
content Emulsion No. (25.degree. C., cps) (%)
______________________________________ Example 1 22,000 14.1 2
17,000 14.4 3 130 9.2 4 21,000 15.1 5 20,000 14.4 6 15,000 15.4 7
20,000 14.1 8 15,000 14.4 9 180 9.2 10 20,000 14.2 11 18,500 14.5
12 150 9.3 13 21,500 15.0 14 21,000 14.3 15 16,100 15.5 16 20,500
14.0 17 14,500 14.4 18 21,000 14.2 19 17,500 14.4 20 140 9.2 21
22,000 14.9 22 20,000 14.4 23 14,600 15.5 24 21,000 14.2 25 15,200
14.5 Comp. Ex. 1 21,000 14.2 2 16,000 14.4 3 140 9.2 4 20,000 14.9
5 19,000 14.4 6 16,000 15.5 7 19,000 14.2 8 17,000 14.5 9 160 9.2
______________________________________
The stability of each of the above emulsions did not vary over 3
months.
Examples 26-50
Various sheet-like porous materials having properties, which will
be described below in Table 4, were obtained respectively by
impregnating and/or coating various base materials with the
polyurethane emulsions shown in Table 2 and then drying the
thus-impregnated and/or coated base materials under conditions
summarized below in Table 3. Comparative Examples 10-18 were
conducted under the same conditions as Examples 26-34.
TABLE 3
__________________________________________________________________________
Emulsion Ex. No. Base material Coated/impregnated amount Drying
conditions
__________________________________________________________________________
26 1 Parting paper Coated at 200 g/m.sup.2 80.degree. C. .times. 2
min + 125.degree. C. .times. 2 min 27 2 Parting paper Coated at 200
g/m.sup.2 80.degree. C. .times. 2 min + 125.degree. C. .times. 2
min 28 3 Nonwoven fabric Impregnated at 1000 g/m.sup.2 90.degree.
C. .times. 3 min + 140.degree. C. .times. 3 min 29 4 Cotton fabric
Coated at 400 g/m.sup.2 140.degree. C. .times. 3 min 30 5 Nylon
taffeta Coated at 200 g/m.sup.2 80.degree. C. .times. 2 min +
125.degree. C. .times. 2 min 31 6 Tufted T/R fabric Coated at 600
g/m.sup.2 120.degree. C. .times. 4 min 32 7 Polyester taffeta
Coated at 200 g/m.sup.2 140.degree. C. .times. 2 min 33 8 Tufted
T/R fabric Coated at 600 g/m.sup.2 120.degree. C. .times. 4 min 34
9 Nonwoven fabric Impregnated at 1000 g/m.sup.2 120.degree. C.
.times. 5 min 35 10 Parting paper Coated at 200 g/m.sup.2
80.degree. C. .times. 2 min + 125.degree. C. .times. 2 min 36 11
Parting paper Coated at 200 g/m.sup.2 80.degree. C. .times. 2 min +
125.degree. C. .times. 2 min 37 12 Nonwoven fabric Impregnated at
1000 g/m.sup.2 90.degree. C. .times. 3 min + 140.degree. C. .times.
3 min 38 13 Cotton fabric Coated at 400 g/m.sup.2 140.degree. C.
.times. 3 min 39 14 Nylon taffeta Coated at 200 g/m.sup.2
80.degree. C. .times. 2 min + 125.degree. C. .times. 2 min 40 15
Tufted T/R fabric Coated at 600 g/m.sup.2 120.degree. C. .times. 4
min 41 16 Polyester taffeta Coated at 200 g/m.sup.2 140.degree. C.
.times. 2 min 42 17 Tufted T/R fabric Coated at 600 g/m.sup.2
120.degree. C. .times. 4 min 43 18 Parting paper Coated at 200
g/m.sup.2 80.degree. C. .times. 2 min + 125.degree. C. .times. 2
min 44 19 Parting paper Coated at 200 g/m.sup.2 80.degree. C.
.times. 2 min + 125.degree. C. .times. 2 min 45 20 Nonwoven fabric
Impregnated at 1000 g/m.sup.2 90.degree. C. .times. 3 min +
140.degree. C. .times. 3 min 46 21 Cotton fabric Coated at 400
g/m.sup.2 140.degree. C. .times. 3 min 47 22 Nylon taffeta Coated
at 200 g/m.sup.2 80.degree. C. .times. 2 min + 125.degree. C.
.times. 2 min 48 23 Tufted T/R fabric Coated at 600 g/m.sup.2
120.degree. C. .times. 3 min 49 24 Polyester taffeta Coated at 200
g/m.sup.2 140.degree. C. .times. 4 min 50 25 Tufted T/R fabric
Coated at 600 g/m.sup.2 120.degree. C. .times. 4
__________________________________________________________________________
min
TABLE 4 ______________________________________ V Property I II III
IV Before After ______________________________________ 26 550
.circle. 9550 -- 100 70 27 410 .circle. 9370 -- 100 70 28 450
.circle. 6930 6000 100 50 29 380 .circle. 8560 6500 100 70 30 450
.circle. 6520 4500 100 50 31 350 .circle. 7230 6000 100 70 32 400
.circle. 7520 5000 100 50 33 370 .circle. 8100 6200 100 50 34 570
.circle. 8210 6000 100 70 35 570 .circle. 8250 -- 100 70 36 450
.circle. 8570 -- 100 70 37 500 .circle. 6140 6000 100 50 38 400
.circle. 8210 6500 100 70 39 510 .circle. 6100 4500 100 50 40 620
.circle. 7000 6000 100 70 41 600 .circle. 7120 5000 100 50 42 650
.circle. 7600 6200 100 50 43 580 .circle. 9150 -- 100 70 44 510
.circle. 9070 -- 100 70 45 530 .circle. 6230 6000 100 70 46 450
.circle. 8360 6500 100 70 47 520 .circle. 6510 4500 100 70 Example
48 650 .circle. 7180 6000 100 70 49 630 .circle. 7080 5000 100 50
50 660 .circle. 7590 6500 100 70 Comparative Example 10 30 .circle.
6270 -- 0 0 11 25 .circle. 5820 -- 0 0 12 35 .DELTA. 4050 4500 0 0
13 40 X 5800 5000 0 0 14 30 X 2960 3500 0 0 15 28 .DELTA. 6100 5000
0 0 16 37 X 6890 3500 0 0 17 31 X 5120 5000 0 0 18 28 .DELTA. 6620
5000 0 0 ______________________________________ Note: I Surface
smoothness (surface durability): Each resin layer was rubbed with
gauze under a load of 500 g. Its surface smoothness is expressed in
terms of strokes counted until the resin layer was broken. II Hand
and feeling: .circle. : soft, .DELTA.: slightly hard, X: hard. III
Moisture permeability (g/m.sup.2 .multidot. 24 hrs, measured by the
procedure prescribed in JIS Z0208B). IV Withstandable water
pressure (mm H.sub.2 O). V Washability (water repellancy both
before and after washing).
* * * * *